Polythiophene compositions for improving organic light-emitting diodes

ABSTRACT

The invention relates to compositions which include: (a) a polythiophene containing repeating units represented by the following general formula (I),  
                 
 
wherein X represents, for example, —CH 2 —CH(CH 2 —O—(CH 2 ) 4 SO 3   − H + )—; and (b) further polymers, that are different than polythiophene (a), and which contain SO 3   −  M +  or COO − M +  groups. Also disclosed are electroluminescing (EL) arrangements that contain hole-injecting layers which include such compositions.

CROSS REFERENCE TO RELATED PATENT APPLICATION

The present patent application claims the right of priority under 35U.S.C. §119 (a)-(d) of German Patent Application No. ______, filed Feb.10, 2004.

FIELD OF THE INVENTION

The present invention relates to compositions/formulations containingpolythiophenes and further polymers, their use, and electroluminescingarrangements containing hole-injecting layers containing theseformulations.

BACKGROUND OF THE INVENTION

An electroluminescing arrangement (EL arrangement) is characterised inthat when an electrical voltage is applied it emits light accompanied bya flow of current. Such arrangements have been known for a long timeunder the description “light-emitting diodes”) (LEDs). The emission oflight is due to the fact that positive charges (“holes”) and negativecharges (“electrons”) recombine with the emission of light.

The LEDs conventionally used in technology all consist to a very largeextent of inorganic semiconductor materials. For some years however ELarrangements have been known whose basic constituents are organicmaterials.

These organic EL arrangements generally contain one or more layers oforganic charge transport compounds.

The principal layer structure of an EL arrangement is as follows:

-   1 Carrier, substrate-   2 Base electrode-   3 Hole-injecting layer-   4 Hole-transporting layer-   5 Emitter layer-   6 Electron-transporting layer-   7 Electron-injecting layer-   8 Top electrode-   9 Contacts-   10 Coating, encapsulation

This structure represents the most detailed case and may be simplifiedby omitting individual layers, so that one layer assumes several tasks.In the simplest case an EL arrangement consists of two electrodesbetween which is arranged an organic layer that fulfils all functions,including the emission of light.

It has been found in practice however that in order to enhance thelight-emitting diode electron-injecting and/or hole-injecting layers inthe electroluminescing assemblies are particularly advantageous.

From EP-A 686 662 it is known to use special mixtures of conductingorganic polymeric conductors such as poly(3,4-ethylenedioxythiophene)and for example polyhydroxy compounds or lactams as electrode inelectroluminescent displays. It has been found in practice however thatthese electrodes do not have a sufficient conductivity, especially forlarge area displays. The conductivity is however sufficient for smalldisplays (luminous area <1 cm²).

From DE-A 196 27 071 it is known to use polymeric organic conductors,for example poly(3,4-ethylenedioxythiophene), as hole-injecting layers.The luminosity of the electroluminescing displays can thereby besignificantly increased compared to structures that do not employpolymeric organic intermediate layers. The conductivity can bespecifically adjusted by reducing the particle size of thepoly(3,4-alkylenedioxythiophene) dispersions. In this way it is possibleto prevent electrical crosstalk between adjacent address lines,especially in passive matrix displays (EP-A 1 227 529).

The service life of these displays is however still not sufficient formany practical applications.

There therefore existed the need to produce EL arrangements that have,in addition to a high luminosity (luminous intensity), a longer servicelife, in particular a longer service life at a high luminosity, thanknown EL arrangements.

SUMMARY OF THE INVENTION

The object of the present invention accordingly consisted in discoveringand providing suitable materials for the production of such ELarrangements. A further object consisted in producing such ELarrangements from these materials.

It was surprisingly found that hitherto unknown formulations containingoptionally substituted polyanilines or polypyrroles or speciallysubstituted polythiophenes and polymers soluble in polar solvents areoutstandingly suitable for producing hole-injecting layers for ELarrangements, and that the resultant EL arrangements have significantlylonger service lives than known EL arrangements.

The present invention accordingly provides compositions/formulationscomprising at least one optionally substituted polyaniline orpolypyrrole or at least one polythiophene containing repeating units ofthe general formula (I),

wherein

-   X denotes —(CH₂)_(x)—CR¹R²—(CH₂)_(y)—, wherein    -   R¹ denotes —(CH₂)_(s)—O—(CH₂)_(p)—R³, where    -   R³ denotes SO₃ ⁻M⁺ or COO⁻M⁺, where M⁺ denotes H⁺, Li⁺, Na⁺, K⁺,        Rb⁺, Cs⁺ or NH₄ ⁺, preferably H⁺, Na^(+ or K) ⁺, particularly        preferably H⁺,    -   s is an integer from 0 to 10, preferably 0 to 3, particularly        preferably 0 or 1, and    -   p is an integer from 1 to 18, preferably 2 to 6, particularly        preferably 3, 4 or 5,    -   or denotes —(CH₂)_(q)—O(CH₂CH₂O)_(r)R⁴,    -   wherein    -   R⁴ denotes optionally substituted C₁-C₄-alkyl,    -   q denotes an integer from 0 to 10, and    -   r denotes an integer from 1 to 12, preferably 2, 3 or 4,-   R² independently of R¹ denotes H, a linear or branched optionally    substituted C₁-C₂₀-alkyl radical, a C₆-C₁₄-aryl radical or    —(CH₂)_(s)—O—(CH₂)_(p)R³ or —(CH₂)_(q)—O(CH₂CH₂O)_(r)R⁴,    -   where R³, s, p, R⁴, q and r have the meanings given for R¹, and-   x, y in each case independently of one another denote an integer    from 0 to 9, preferably 0 to 3, particularly preferably 0, 1 or 2,    and at least one further polymer containing SO₃ ⁻M⁺, or COO⁻M⁺    groups, where M⁺ denotes H⁺, Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺ or NH₄ ⁺,    preferably H⁺, Na⁺ or K⁺, particularly preferably H⁺.

Here and below the term substituted means if not otherwise indicated asubstitution with chemical group selected from the group consisting of:

-   -   alkyl, in particular C₁-C₂₀-alkyl, cycloalkyl, in particular        C₃-C₂₀-cycloalkyl, aryl, in particular C₆-C₁₄-aryl, halogen, in        particular Cl, Br, J, ether, thioether, disulfide, sulfoxide,        sulfone, amino, aldehyde, keto, carboxylic acid ester, cyano,        alkylsilane and alkoxysilane groups as well as carboxylamide        groups.

Unless otherwise indicated, all numbers or expressions, such as thoseexpressing quantities of ingredients, process conditions, etc., used inthe specification and claims are understood as modified in all instancesby the term “about.”

DETAILED DESCRIPTION OF THE INVENTION

The repeating units of the general formula (I) may be identical ordifferent within a polythiophene. Preferred are repeating units of thegeneral formulae (I-a) and/or (I-b),

wherein R¹ and R² have the meanings given hereinbefore for the generalformula (I).

Preferred embodiments of the present invention are such formulationscontaining at least one polythiophene containing repeating units of theformulae (I-a-1) and/or (I-b-1) and/or (I-a-2) and/or (I-b-2)

In the case where repeating units of the general formulae (I-a) and/or(I-b) and/or (I-a-1) and/or (I-b-1) and/or (I-a-2) and/or (I-b-2) arecontained in the polythiophene, the radicals R¹ may in each case beidentical or different and the radicals R² may in each case be identicalor different, though preferably the radicals R¹ are in each caseidentical and the radicals R² are in each case identical.

The polythiophene may be built up from repeating units of the generalformula (I -a), (I-a-1) and/or (I-a-2) or from repeating units of thegeneral formula (I-b), (1-b-1) and/or (I-b-2) or also from repeatingunits of the general formula (I-a) and (I-b), (I-a-1) and (I-b-1) and/or(I-a-2) and (I-b-2). In the last-mentioned case the units of the generalformula (I-a) and (I-b), (I-a-1) and (I-b-1) and/or (I-a-2) and (I-b-2)may be contained in arbitrary proportions in the polythiophene, thoughpreferably the units of the general formula (I-a), (I-a-1) and/or(I-a-2) are contained in a proportion of 65 to 99.5%, particularlypreferably in a proportion of 75 to 99% and most particularly preferablyin a proportion of 75 to 85%, referred to the total content of repeatingunits in the polythiophene, and the units of the general formula (I-b),(I-b-1) and/or (I-b-2) are contained preferably in a proportion of 0.5to 35%, particularly preferably in a proportion of 1 to 25% and mostparticularly preferably in a proportion of 15 to 25%, referred to thetotal number of repeating units in the polythiophene, with the provisothat the sum total of both proportions is 100%.

The polythiophene may however contain, in addition to the repeatingunits of the general formula (I), (I-a) and/or (I-b), (I-a-1) and/or(I-b-1) and/or (I-a-2) and/or (I-b-2), also other repeating units, forexample repeating units of the general formulae (II) and/or (III),

wherein

-   A denotes an optionally substituted C₁-C₅-alkyl radical,-   R denotes a linear or branched, optionally substituted C₁-C₁₈-alkyl    radical, an optionally substituted C₅-C₁₂-cycloalkyl radical, an    optionally substituted C₆-C₁₄-aryl radical, an optionally    substituted C₇-C₁₈-aralkyl radical, an optionally substituted    C₁-C₄-hydroxyalkyl radical or an hydroxyl radical,-   x denotes an integer from 0 to 8, and    in the case where several radicals R are bonded to A, these may be    identical or different.

As optional further substituents of the radical R, numerous organicgroups are suitable, for example alkyl, cycloalkyl, aryl, halogen,ether, thioether, disulfide, sulfoxide, sulfone, amino, aldehyde, keto,carboxylic acid ester, cyano, akylsilane and alkoxysilane groups as wellas carboxylamide groups.

The polythiophene may contain, apart from the repeating units of thegeneral formula (I), (I-a) and/or (I-b), (I-a-1) and/or (I-b-1) and/or(I-a-2) and/or (I-b-2), preferably also repeating units of the formula(IIIa), (3,4-ethylenedioxythiophene units)

In preferred embodiments of the formulations according to the inventionR² in the repeating units of the general formula (I), (I-a) and/or (I-b)denotes H.

In further preferred embodiments of the formulations according to theinvention R³ in the repeating units of the general formula (I), (I-a)and/or (I-b) denotes SO₃ ⁻M⁺, where M⁺ has the meaning mentionedhereinbefore for the general formula (I).

In the case where the polythiophenes are copolymers of two or moredifferent repeating units of the general formula (I)— here andhereinafter this is also understood to denote units of the generalformulae (I-a) and/or (I-b) or (I-a-1) and/or (I-b-1) or (I-a-2) and/or(I-b-2)—or repeating units of the general formula (I) and (II) and/or(III)— here and hereinafter also understood to include units of thegeneral formulae (III-a)—the repeating units may be contained randomly,alternatingly or as blocks in the copolymer.

Both in the copolymers containing repeating units of the general formula(I) and optionally further repeating units of the general formulae (II)and/or (III) and also in the homopolymers containing repeating units ofthe general formula (I), the coupling of the repeating units may beregioregular and/or non-regioregular.

The repeating units of the general formulae (II) and/or (III),preferably of the formula (III-a), in a copolymer comprising structuralunits of formular (I) and (II) und/or (III) are contained in thecopolymers preferably in a proportion of at most 50%, particularlypreferably of at most 30%, referred to the total number of the repeatingunits in the copolymer. The repeating units of the general formula (I)are contained in the copolymers in a proportion of at least 50%,preferably in a proportion of at least 70%, referred to the total numberof the repeating units. In this connection repeating units of thegeneral formula (I-a) or (I-b) or (I-a) and (I -b) may be contained.Repeating units of the general formula (I-a) and (I-b) may be containedin arbitrary mixture ratios. Preferably repeating units of the generalformula (I-a) are contained in a proportion of 65 to 100%, particularlypreferably in a proportion of 75 to 99%, most particularly preferably ina proportion of 75 to 85%, referred to the total number of the repeatingunits of the general formula (I), and the repeating units of the generalformula (I-b) are contained in a proportion of 0 to 35%, particularlypreferably in a proportion of 1 to 25% and most particularly preferablyin a proportion of 15 to 25%, referred to the total number of therepeating units of the general formula (I) in the copolymers, with theproviso that the sum total of both proportions is 100%.

The polythiophenes preferably carry in each case H on the terminalgroups. The polythiophenes contain in total n repeating units of thegeneral formula (I) and optionally of the general formulae (II) and/or(III), where n is an integer from 2 to 1000, preferably 3 to 100,particularly preferably 4 to 15.

Repeating units are understood within the context of the invention todenote units of the general formulae (I), (II) or (III), irrespective ofwhether they are contained once or more than once in the polythiophene.In other words, units of the general formulae (I), (II) or (III) arealso understood to be repeating units even if they are contained onlyonce in the polythiophene.

Formulations according to the invention may also include those thatcontain, apart from at least one of the polythiophenes describedhereinbefore containing repeating units of the general formula (I), alsofurther conducting polymers, such as for example polyanilines orpolypyrroles.

The production of the polythiophenes described hereinbefore containingrepeating units of the general formula (I) is described in principle inEP-A 1 122 274 or U.S. Pat. No. 5,111,327.

The polymerisation of the corresponding monomeric compounds usually iscarried out with suitable oxidising agents in suitable solvents.Examples of suitable oxidising agents are iron(III) salts, in particularFeCl₃ and iron(III) salts of aromatic and aliphatic sulfonic acids,H₂O₂, K₂Cr₂O₇, K₂S₂O₈, Na₂S₂O₈, KMnO₄, alkali metal perborates andalkali metal or ammonium persulfates or mixtures of these oxidisingagents. Further suitable oxidising agents are described for example in“Handbook of Conducting Polymers” (Ed. Skotheim, T. A.), Marcel Dekker:New York, 1986, Vol. 1, 46-57. Particularly preferred oxidising agentsare FeCl₃, Na₂S₂O₈ and K₂S₂O₈ or mixtures thereof. The polymerisation ispreferably carried out at a reaction temperature of −20° to 100° C.Particularly preferred are reaction temperatures of 20° to 100° C. Thereaction solution is then optionally treated with at least one ionexchanger.

Suitable solvents are for example polar solvents such as for examplewater, alcohols such as methanol, ethanol, 2-propanol, n-propanol,n-butanol, diacetone alcohol, ethylene glycol, glycerol or mixtures ofthese. Also suitable are aliphatic ketones such as acetone and methylethyl ketone, aliphatic nitrites such as acetonitrile, aliphatic andcyclic amides such as N,N-dimethylacetamide, N,N-dimethylformamide (DMF)and 1-methyl-2-pyrrolidone (NMP), ethers such as tetrahydrofuran (THF)as well as sulfoxides such as dimethyl sulfoxide (DMSO) or mixture ofthese solvents with one another or with the previously specifiedsolvents.

The corresponding monomeric compounds for the production ofpolythiophenes containing repeating units of the general formula (I) areknown. Their production is described for example in Chevrot et al., J.Electroanal. Chem. 1998, 443, 217-226, Leclerc et al., Adv. Mater. 1997,9, 1087-1094 and Reynolds et al., Polymer Preprints 1997, 38 (2), 320.

The resulting polythiophenes are readily soluble in the polar solventsor solvent mixtures.

The formulations according to the invention contain at least one furtherpolymer containing SO₃ ⁻M⁺ or COO⁻M⁺ groups. Suitable polymers withinthe scope of the invention containing SO₃ ⁻M⁺ or COO⁻M⁺ groups arepreferably those that do not contain a completely conjugated main chain,hereinafter also briefly termed non-conjugated. Preferably thesepolymers are soluble in polar solvents such as water, alcohols such asmethanol, ethanol, 2-propanol, n-propanol, n-butanol, diacetone alcohol,ethylene glycol, glycerol, aliphatic ketones such as acetone and methylethyl ketone, aliphatic nitrites such as acetonitrile, aliphatic andcyclic amides such as N,N-dimethylacetamide, N,N-dimethylformamide (DMF)and 1-methyl-2-pyrrolidone (NMP), ethers such as tetrahydrofuran (THF)as well as sulfoxides such as dimethyl sulfoxide (DMSO) or mixturescontaining these, preferably in water, alcohols such as methanol,ethanol, 2-propanol, n-propanol and n-butanol or mixtures thereof.

Suitable polymers containing SO₃ ⁻M⁺ or COO⁻M⁺ groups that may bementioned by way of example are polymeric carboxylic acids such aspolyacrylic acids, polymethacrylic acid or polymaleic acids, orpolymeric sulfonic acids such as polystyrenesulfonic acids andpolyvinylsulfonic acids. Also suitable are copolymers of vinylcarboxylicand vinylsulfonic acids with other polymerisable monomers such asacrylic acid esters and styrene, or polymers containing partiallyfluorinated or perfluorinated SO₃ ⁻M⁺ or COO⁻M⁺ groups. Particularlysuitable are polystyrenesulfonic acid, poly(styrenesulfonic co-maleicacid), poly(vinylsulfonic acid) or commercially obtainable polymers thatcontain sulfonic acid groups and CF₂ groups, such as for exampleNafion®, (copolymer of tetrafluoroethylene and of the fluorovinyletherof poly(hexafluoro propylene oxide)mono(tetrafluoro vinyl sulfonicacid)ethers).

In preferred embodiments the formulation according to the inventioncontains as at least one polymer containing SO₃ ⁻M⁺ or COO⁻M⁺ groups, apartially fluorinated or perfluorinated polymer containing SO₃ ⁻M⁺ orCOO⁻M⁺ groups.

Such polymers containing partially fluorinated or perfluorinated SO₃ M⁺or COO⁻M⁺ groups are for example those containing repeating units of theformulae (IV-a) and (IV-b),

wherein R_(f) denotes a radical with at least one, preferably 1 to 30,repeating unit(s) of the formula (IV-c)

Such perfluorinated polymers are for example the polymers obtainablecommercially under the trade name Nafion® or in dissolved form under thetrade name Liquion®.

In particularly preferred embodiments the formulation according to theinvention contains Nafion® (copolymer of tetrafluoroethylene and of thefluorovinylether of poly(hexafluoro propylene oxide)mono(tetrafluorovinyl sulfonic acid)ethers) as at least one polymer containing SO₃ ⁻M⁺or COO⁻M⁺ groups.

In further preferred embodiments the formulation according to theinvention contains at least two polymers containing SO₃ ⁻M⁺ or COO⁻M⁺groups. In a particularly preferred embodiment the formulation accordingto the invention contains copolymers of tetrafluroethylene and sulfonicacid or carboxyl functional perfluorinated ethylene (e.g., Nafion® PFSApolymers) and polystyrenesulfonic acid (PSS) as polymers containing SO₃⁻M⁺ or COO⁻M⁺ groups.

The molecular weight of the polyacids is preferably 1,000 to 2,000,000,particularly preferably 2,000 to 500,000. The polyacids or their alkalimetal salts are commercially available, for example polystyrenesulfonicacids and polyacrylic acids, or may however also be produced by knownprocesses (see for example Houben Weyl, Methoden der organischen Chemie,Vol. E 20 Makromolekulare Stoffe, Part 2, (1987), p. 1141 ff.).

The formulations according to the invention contain, referred to onepart by weight of polythiophene(s) containing repeating units of thegeneral formula (I), preferably 1 to 30 parts by weight, particularlypreferably 2 to 15 parts by weight of the polymer or polymers containingSO₃ ⁻M⁺ or COO⁻M⁺ groups. Most particularly preferably the formulationsaccording to the invention contain the polythiophene or polythiophenescontaining repeating units of the general formula (I) and the polymer orpolymers containing SO₃ ⁻M⁺ or COO⁻M⁺ groups, in a weight ratio ofpolythiophene(s) to polymer(s) containing SO₃ ⁻M⁺ or COO⁻M⁺ groups of 1to 2 (1:2) to 1 to 15 (1:15), in particular 1 to 3 (1:3) to 1 to 15(1:15).

This ratio of polythiophene(s) to polymer(s) containing SO₃ ⁻M⁺ orCOO⁻M⁺ groups may be adjusted directly by mixing the two components.

Furthermore the formulations according to the invention may preferablycontain at least one polar diluent. Polar diluents (solvents) within thescope of the invention are understood to mean diluents with a solubilityparameter 6 of 16 MPa^(1/2) and above, preferably 19 MPa^(1/2) andabove. The measurement of solubility parameters as a rule takes place atstandard temperature (20° C.). For the measurement and calculation ofsolubility parameters, see J. Brandrup et al., Polymer Handbook, 4^(th)Edition, 1999, VII/675-VII/688. Solubility parameters are tabulated, forexample in J. Brandrup et al., Polymer Handbook, 4^(th) Edition, 1999,VII/688-VII/697. Preferred polar diluents are water, alcohols such asmethanol, ethanol, 2-propanol, n-propanol, n-butanol, diacetone alcohol,ethylene glycol, glycerol, aliphatic ketones such as acetone and methylethyl ketone, aliphatic nitrites such as acetonitrile, aliphatic andcyclic amides such as N,N-dimethylacetamide, N,N-dimethylformamide (DMF)and 1-methyl-2-pyrrolidone (NMP), ethers such as tetrahydrofuran (THF)as well as sulfoxides such as dimethyl sulfoxide (DMSO) or mixturescontaining these. Particularly preferred polar solvents are water,alcohols or mixtures containing these, most particularly preferred beingwater, methanol, ethanol, n-propanol, 2-propanol or n-butanol ormixtures containing these.

Such new formulations containing at least one polar diluent preferablycontain 99.99 to 80 wt. %, particularly preferably 99.8 to 95 wt. % ofpolar diluent(s) and have a solids content of 0.01 to 20 wt. %,particularly preferably 0.2 to 5 wt. %, i.e. they contain in total 0.01to 20 wt. %, particularly preferably 0.2 to 5 wt. % of polythiophene(s),polymer(s) containing SO₃ ⁻M⁺ or COO⁻M⁺ groups, and optionally furthercomponents such as e.g. binders, crosslinking agents and/or surfactantsin dissolved and/or dispersed form.

The viscosity at 20° C. of the new formulations containing at least onepolar diluent is typically between the viscosity of the diluent and 200mPas, preferably <100 mPas.

In order to adjust the desired solids content and the necessaryviscosity, the desired amount of diluent can be removed from theformulations by distillation, preferably in vacuo, or by other methods,e.g. filtration.

Organic, polymeric binders and/or organic, low molecular weightcrosslinking agents or surfactants may also be added to the formulationsaccording to the invention. Suitable binders are described for examplein EP-A 564 911. By way of example there may be mentionedpolyvinylcarbazole, silanes such as Silquest® A187 (OSi specialities) orsurfactants such as the fluorinated surfactant FT 248 (Bayer AG,tetraethylammonium salt of perfluoro octyl sulfonic acid).

The formulations preferably contain only minor amounts of ionicimpurities within the limits as described in EP-A 991 303. Preferablythe formulations contain less than 1000 ppm of ionic impurities.

The formulations according to the invention may be produced in variousways. For example, it is possible to mix at least one polythiophene withat least one polymer containing SO₃ ⁻M⁺ or COO⁻M⁺ groups and optionallyadd at least one diluent to this mixture, and preferably dissolve itcompletely or partially in at least one diluent. It is also possible todissolve at least one polythiophene beforehand in at least one diluentand to dissolve at least one polymer containing SO₃ ⁻M⁺ or COO⁻M⁺ groupsbeforehand in at least one diluent and then to mix the two solutions.The diluent or diluents may then optionally be completely or partiallyremoved from this mixture, for example by distillation or by othermethods. There also exists the possibility of producing the formulationsaccording to the invention by first of all producing the polythiopheneor polythiophenes by polymerisation of the corresponding monomericcompounds with at least one suitable oxidising agent in at least onesuitable solvent, wherein either the solvent corresponds to one of thepolar diluents listed hereinbefore or an appropriate exchange of solventor addition of further solvents may take place after completion of thepolymerisation. At least one polymer containing SO₃ ⁻M⁺ or COO⁻M⁺groups—optionally likewise dissolved in at least one diluent—may then bemixed with the polythiophene solution and added to this solution. Thediluent or diluents may then optionally be removed completely orpartially from this mixture.

Surprisingly the formulations according to the invention areoutstandingly suitable for the production of hole-injecting orhole-transporting layers in EL arrangements, organic solar cells,organic laser diodes, organic thin film transistors or organic fieldeffect transistors, and for the production of electrodes or electricallyconducting coatings.

The present invention accordingly also provides for the use of theformulations according to the invention for the production ofhole-injecting layers in EL arrangements, and for the production ofelectrodes or electrically conducting coatings.

In particular EL arrangements with a hole-injecting layer containing aformulation according to the invention are characterised by a highluminosity (luminous intensity) and a significantly longer service lifethan known EL arrangements.

The present invention accordingly also provides EL arrangementscomprising a hole-injecting layer on the basis of a formulationaccording to the invention.

Preferred are those EL arrangements comprising at least two electrodes,at least one of which is optionally mounted on an optionally transparentsubstrate, at least one emitter layer between the two electrodes and atleast one hole-injecting layer between one of the two electrodes and theemitter layer, characterised in that the hole-injecting layer contains aformulation according to the invention.

In the production of many large-area EL arrangements, for examplelarge-area electroluminescing display elements, it is advantageous if atleast one of the current-conducting electrodes consists of a transparentand conducting material.

Suitable as such transparent and conducting electrode materials are forexample

-   -   a) metal oxides, e.g. indium-tin oxide (ITO), tin oxide (NESA),        doped tin oxide, doped zinc oxide, etc.,    -   b) semi-transparent metals films, e.g. Au, Pt, Ag, Cu etc.,    -   c) semi-transparent, conducting polymers, e.g. polythiophenes,        polyanilines, polypyrroles, etc.

In the case of an electrode that does not consist of one of thetransparent and conducting materials listed hereinbefore, then it ispreferably a metal electrode, in particular a metal cathode.

Suitable materials for metal cathodes are those commonly used forelectrooptical structures and known to the person skilled in the art.Suitable as metal cathodes are preferably those of metals with a lowwork function such as Mg, Ca, Ba or metal salts such as LiF.

Suitable as optionally transparent substrate are for example glass, verythin glass (flexible glass) or plastics, preferably plastics films.

Particularly suitable plastics are: polycarbonates, polyesters such ase.g. PET and PEN (polyethylene terephthalate and polyethylenenaphthalenedicarboxylate), copolycarbonates, polyacrylate, polysulfone,polyether sulfone (PES), polyimide, polyethylene, polypropylene orcyclic polyolefins and cyclic olefin copolymers (COC), hydrogenatedstyrene polymers or hydrogenated styrene copolymers.

Suitable polymer substrates may for example be films such as polyesterfilms, PES films from Sumitomo, or polycarbonate films from Bayer AG(Makrofol®).

A bonding agent layer may be arranged between the substrate and theelectrode. Suitable bonding agents are for example silanes. Preferredare epoxysilanes, such as for example 3-glycidoxypropyltrimethoxysilane(Silquest® A187, OSi specialities). Other bonding agents withhydrophilic surface properties may also be used. Thus, for example, athin layer of PEDT:PSS is described as a suitable bonding agent for PEDT(Hohnholz et al., Chem. Commun. 2001, 2444-2445).

The emitter layer of the EL arrangement according to the inventioncontains at least one emitter material. Suitable emitter materials arethose commonly used for electrooptical structures and known to theperson skilled in the art. Suitable emitter materials are preferablyconjugated polymers such as polyphenylenevinylenes and/or polyfluorenes,such as the polyparaphenylenevinylene derivatives and polyfluorenederivatives described for example in WO-A 90/13148, or emitters from theclass of low molecular weight emitters, also termed “small molecules” inspecialist circles, such as aluminium complexes, e.g.tris(8-hydroxy-quinolinato)aluminium (Alq₃), fluorescing dyes, e.g.quinacridones, or phosphorescing emitters, e.g. Ir(ppy)₃. Emittermaterials are described for example in DE-A 196 27 071.

In addition to the layers listed hereinbefore, further functional layersmay be contained in such an electroluminescing layer structure (ELarrangement), such as for example further charge-injecting, e.g.electron-injecting, charge-transporting or charge-blocking intermediatelayers. Such layer composites are known to the person skilled in the artand are described for example in J. R. Sheats et al., Science 273,(1996), 884. A layer may also perform several tasks. For example, theemitter materials listed hereinbefore may be used in combination with ahole-transporting intermediate layer between the hole-injecting andemitter layer (cf. e.g. U.S. Pat. No. 4,539,507 and U.S. Pat. No.5,150,006).

The basic production of such EL arrangements is known to the personskilled in the art. They may be produced for example by applying anelectrode from solution or by vapour deposition on a substrate. Forexample, metal oxide electrodes or semi-transparent metal filmelectrodes are preferably applied by vapour deposition, whereassemi-transparent, conducting polymer electrodes are preferably appliedfrom solution to the substrate. A bonding agent may optionally beapplied—by vapour deposition or from solution—before application of theelectrode material to the substrate. Some examples of substrates coatedwith electrode material are also already commercially obtainable (e.g.K-Glas, ITO-coated glass substrates). The hole-injecting layer may thenbe applied to the electrode, which advantageously takes place fromsolution in the case of the EL arrangements according to the inventionwith a hole-injecting layer containing a formulation according to theinvention. The further layers are then applied from solution or byvapour deposition, depending on the material used, to the hole-injectinglayer in the order specified in the introduction, bearing in mind thatindividual layers may be omitted. The layer arrangement is thencontacted and encapsulated.

The production of the hole-injecting layer containing a formulationaccording to the invention is carried out according to known techniques.For this, a formulation according to the invention—optionally in asolvent—is applied as a film to an electrode, preferably the baseelectrode. Suitable solvents are the polar diluents specified above,preferably water, alcohols or mixtures of the latter. Suitable alcoholsare for example methanol, ethanol, n-propanol, 2-propanol and n-butanol.

The use of these solvents has the advantage that further layers may beapplied from organic solvents such as aromatic or aliphatic hydrocarbonmixtures without the hole-injecting layer being attacked.

The formulation according to the invention—optionally in a solvent—maybe uniformly distributed on the electrode by techniques such as spincoating, casting, knife application, pressure application, curtaincasting, etc. The layers may then be dried at room temperature ortemperatures of up to 300° C., preferably 100° to 200° C.

The formulation according to the invention—optionally in a solvent—mayalso preferably be applied in a structured manner by techniques such asinkjet application. This technique is known to the person skilled in theart and is described, with the use of water-soluble and dispersedpolythiophenes such as3,4-polyethylenedioxythiophene:polystyrenesulfonic acid (PEDT:PSS), forexample in Science, Vol. 279, 1135, 1998 and DE-A 198 41 804.

Preferably the formulations according to the invention—optionally in asolvent—are filtered through a filter before the application.

Formulations that can be filtered particularly well are for exampleobtained if, referred to one part by weight of polythiophene(s)containing repeating units of the general formula (I), there arepreferably used 1 to 30 parts by weight, particularly preferably 2 to 15parts by weight of the polymer(s) containing SO₃ ⁻M⁺ or COO⁻M⁺ groups,and most particularly preferably the formulations according to theinvention contain the polythiophene(s) containing repeating units of thegeneral formula (I) and the polymer(s) containing SO₃ ⁻M⁺ or COO⁻M⁺groups, in a weight ratio of polythiophene(s) to polymer(s) containingSO₃ ⁻M⁺ or COO⁻M⁺ groups of 1 to 2 to 1 to 15.

The thickness of the hole-injecting layer is for example 3 to 500 nm,preferably 10 to 200 nm.

The influence of a hole-injecting layer containing a formulationaccording to the invention on the properties of the EL arrangement maybe tested in a special assembly of such an EL arrangement according tothe invention. For this, the hole-injecting layer is applied by means ofa spin coater to a wet chemically cleaned ITO substrate. The layer isthen dried at 100°-200° C. for 5 minutes. The layer thickness is 20-300nm. Depending on the spinning speed, a 1 wt. % solution of apolyfluorene-based emitter material (Green 1300 LUMATION™ from DowChemical Company) in xylene is spin centrifuged as emitter layer. Thethickness of the emitter layer is typically 60-120 nm. Finally, ascathode a 5 nm thick Ba layer is vapour deposited and a 200 nm thick Aglayer is then vapour deposited thereon. By contacting the indium/tinoxide (ITO) anode and the metal cathode, current/voltage/luminous fluxdensity characteristic lines are recorded by means of a characteristicline recorder and a calibrated photodiode and the service lives aremeasured. For this, a constant electric current or an alternatingcurrent is passed through the arrangement and the voltage and theluminous flux density are followed over time.

The organic light-emitting diodes according to the invention arecharacterised by a long service life, high luminosity, low appliedvoltages and a high rectification ratio. Compared to knownlight-emitting diodes with hole-injecting layers produced from apoly(3,4-ethylenedioxythiophene):polystyrenesulfonic acid (PEDT:PSS)dispersion (Baytron® P, H. C. Starck GmbH), it was surprisingly foundthat the service lives of organic light-emitting diodes according to theinvention with a hole-injecting layer containing a formulation accordingto the invention are significantly longer.

EXAMPLES Example 1 Production of a Polymer Containing4˜(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-ylmethoxy)-1-butanesulfonicacid) repeating units and4-(3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-3-yl)-1-butanesulfonicacid) repeating units (PEDT-S)

17.5 g of EDT-S (mixture of 80% of4-(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-ylmethoxy)-1-butanesulfonicacid and 20% of4-(3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-3-yl)-1-butanesulfonicacid) as sodium salt were dissolved in 350 ml of water under aprotective gas atmosphere (N₂). 25.6 g of FeCl₃ wre then added. Thesolution was next stirred for 2 hours at room temperature (=RT, 23° C.),then heated at 100° C. for 12 hours, and worked up after cooling to RT.For this, the solution was diluted with water to ca. 3 wt. % anddeionised with 66 g each of Lewatit® S 100 (cation exchanger from BayerChemicals AG) and Lewatit® MP 62 (anion exchanger from Bayer ChemicalsAG) by stirring for 4 hours at 23° C. This procedure was repeated afurther three times. Solids content: 1.45 wt. % Iron content: 1.7 ppmSodium content: 32 ppm Sulfate content: 15 ppm Chloride content: <10 ppm

The sodium salt of the EDT-S used was prepared from Baytron® M OH VP CH8020 (mixture of 80% of2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl-methanol and 20% of3,4-dihydro-2H-thieno-[3,4-b][1,4]dioxepin-3-ol, H. C. Starck GmbH)similarly to the procedure described by Chevrot et al., J. Electroanal.Chem. 1998, 443, pp. 217-226. According to ¹H-NMR analysis in D₂O theproduct consists of 80% of4-(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-ylmethoxy)-1-butanesulfonicacid and 20% of4-(3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-3-yl)-1-butanesulfonicacid, in each case as the sodium salt.

Example 2.1

20 g of the PEDT-S solution prepared according to Example 1 with asolids content of 1.45 wt. % are mixed with 36.4 g of a 4.78 wt. %solution of Nafion® in a mixture of lower aliphatic alcohols and water(Nafion® perfluorinated ion-exchange resin, 5 wt % solution in loweraliphatic alcohols/H₂O″, CAS-No. 66796-30-3, Aldrich Order No. 27,470-4,measured solids content 4.78 wt. %). The weight ratio of PEDT-S toNafion® is in this solution 1:6.

Example 2.2

20 g of the PEDT-S solution prepared according to Example 1 with asolids content of 1.45 wt. % are mixed with 15.17 g of a 4.78 wt. %solution of Nafion® in a mixture of lower aliphatic alcohols and water(Nafion® perfluorinated ion-exchange resin, 5 wt % solution in loweraliphatic alcohols/H₂O″, CAS-No. 66796-30-3, Aldrich Order No. 27,470-4,measured solids content 4.78 wt. %). The weight ratio of PEDT-S toNafion® is in this solution 1:2.5.

Example 2.3

The PEDT-S solution from Example 1 is mixed with different amounts of asolution of polystyrenesulfonic acid (PSS) in H₂O (HAPPS VP AI 4061,solids content 5.88 wt. %, H. C. Starck GmbH). Weight Ratio PEDT-S:PSSComposition of the Solution for Stage 2 1:1  21.1 g of PEDT-S solutionwith 1.45 wt. % solids content,  5.2 g of PSS solution with 5.88 wt. %solids content,   1:2.5 10.55 g of PEDT-S solution with 1.45 wt. %solids content,  6.37 g of PSS solution with 5.88 wt. % solids content,1:6 10.55 g of PEDT-S solution with 1.45 wt. % solids content, 15.61 gof PSS solution with 5.88 wt. % solids content,

Example 3

The formulation according to the invention from Example 2.1 is used toconstruct an organic light-emitting diode (OLED). The followingprocedure is adopted in the production of the OLED:

1. Cleaning of the ITO-Coated Substrate

ITO-coated glass. (Merck Balzers AG, FL, Part. No. 253 674 XO) is cutinto 50 mm×50 mm size pieces (substrates). The substrates are thencleaned in a 3% aqueous mucasol solution in an ultrasound bath for 15minutes. Following this the substrates are rinsed with distilled waterand spin-dried in a centrifuge. This rinsing and drying procedure isrepeated 10 times. The ITO-coated sides are cleaned for 10 minutes in aUV/ozone reactor (PR-100, UVP Inc., Cambridge, GB) immediately beforethe coating.

2. Application of the Hole-Injecting Layer

About 10 ml of the mixture according to the invention from Example 2.1are filtered (Millipore HV, 0.45 μm). The cleaned ITO-coated substrateis placed on a paint application centrifuge and the filtered solution isdistributed on the ITO-coated side of the substrate. The supernatantsolution is then spun off by rotating the plate at 1200 rpm for a periodof 30 seconds. Following this the coated substrate is dried for 5minutes at 200° C. on a hotplate. The layer thickness is 85 nm (Tencor,Alphastep 500).

3. Application of the Emitter Layer

5 ml of a 1 wt. % xylene solution of the emitter Green 1300 LUMATION™(Dow Chemical Company) are filtered (Millipore HV, 0.45 μm) anddistributed on the dried, hole-injecting layer. This and all furtherprocess steps are carried out in an atmosphere of pure nitrogen (inertgas-glove box system, M. Braun, Garching). The hole-injection layer ispost-dried beforehand in the glove box for a further 5 minutes at 200°C. The supernatant solution of the emitter is then spun off by rotatingthe plate at 400 rpm for 30 seconds. Following this the coated substrateis dried for 15 minutes at 130° C. on a hotplate. The total layerthickness is 185 nm.

4. Application of the Metal Cathode

A metal cathode is vapour deposited on the emitter layer. The substrateis placed together with the emitter layer downwards on a perforated mask(hole diameter 2.5 mm). A 5 nm thick Ba layer and a 200 nm thick Aglayer are vapour deposited in succession from two vapour depositionboats at a pressure of p=10⁻³ Pa. The vapour deposition rates are 10Å/sec for Ba and 20 Å/sec for Ag.

5. Characterisation of the OLED

The two electrodes of the organic LED are connected (contacted) viaelectrical leads to a voltage source. The positive pole is connected tothe ITO electrode and the negative pole to the metal electrode. Thedependence of the OLED current and elecroluminescence intensity(detection by means of a photodiode (EG&G C30809E) on the voltage arerecorded. The service lives are then determined by passing a constantcurrent I=0.39 mA (8 mA/cm²) through the arrangement and following thevoltage and light intensity over time. All OLED characterisations arecarried out in the glove box under inert conditions.

Comparison Example 3.1

Production of an OLED withpolyethylenedioxythiophene/polystyrenesulfonic acid as hole-injectinglayer:

The procedure is carried out as in Example 3, with the followingvariation in process step 2:

2. Application of the Hole-Injection Layer

About 10 ml of a 1.3% polyethylenedioxythiophene/polystyrenesulfonicacid solution (Baytron®P, TP AI 4083; manufacturer H. C. Starck GmbH),which had been desalted beforehand by column chromatography, werefiltered (Millipore HV, 0,45 μm). The ITO-coated substrate is thenplaced on a paint application centrifuge and the filtered solution isdistributed over the ITO-coated side of the substrate. The supernatantsolution is then spun off by rotating the plate at 1500 rpm over aperiod of 30 seconds. Following this the coated substrate is dried for 5minutes at 200° C. on a hotplate. The layer thickness is 85 nm.

The application of the metal cathodes according to process step 4 wascarried out jointly with the layer structures from Example 3, in orderto ensure comparability.

Results of the characterision of the OLEDs from Example 3 and ComparisonExample 3.1: t = 0 t = 800 hours U/[V] L/[rel. units] U/[V] L/[rel.units] OLED from Example 3 3.57 1.83 4.25 1.63 OLED from 3.67 1.74 4.460.59 Comparison example 3.1

The voltage U and luminous intensity L, measured as photodiode current,at the start of the service life test (t=0), are compared with thecorresponding values after 800 hours (t=800 hours) under a constantcurrent load I=8 mA/cm².

A comparison of the two OLEDs shows that the OLED according to theinvention from Example 3 with the hole-injecting layer containing theformulation according to the invention has a significantly longerservice life in operation than the OLED from Comparison Example 3.1 withthe hole-injecting layer of known material (PEDT-PSS).

Example 4

The formulation according to the invention from Example 2.1 is used toconstruct an organic light-emitting diode (OLED). In the production ofthe OLED the same procedure as in Example 3 is adopted, with thefollowing difference in the process steps 1., 4. and 5.

Instead of ITO substrates coated over the whole surface (cf. Example 3,process step 1.), structured ITO substrates are used. The ITO structuresconsist of 2.0 mm wide strips insulated from one another. Thestructuring of the ITO was carried out by a conventional photoresisttechnique followed by etching in FeCl₃ solution.

Instead of using a perforated mask (cf. Example 3, process step 4) themetal cathode is vapour deposited through a strip mask that is alignedperpendicular to the ITO strips. The width of the strips is 2 mm. Theactive luminous area at the point of intersection of the two electrodesis 4 mm².

Instead of a constant current and operation with direct current (DCoperation) (cf. Example 3, process step 5), a special alternatingvoltage is applied to the arrangements for the service lifemeasurements. The frequency of the alternating voltage is 100 Hz. Aconstant current of 640 μA flows during the positive half-wave, whereasa voltage of −10 V is applied during the negative half-wave. The cycleratio of positive to negative half-wave is 50:50. The integral areacurrent density is 8 mA/cm².

Comparison Example 4.1

Production of an OLED withpolyethylenedioxythiophene/polystyrenesulfonic acid as hole-injectinglayer:

The procedure is carried out as in Example 4, with the followingvariation in process step 2.:

2. Application of the Hole-Injection Layer

About 10 ml of a 1.3% polyethylenedioxythiophene/polystyrenesulfonicacid solution (Baytron® P, TP AI 4083, weight ratio PEDT:PSS of 1:6;manufacturer H. C. Starck GmbH) are filtered (Millipore HV, 0.45 μm).The ITO-coated substrate is then placed on a paint applicationcentrifuge and the filtered solution is distributed on the ITO-coatedside of the substrate. The supernatant solution is then centrifuged offby rotating the plate at 1500 rpm for a period of 30 seconds. Followingthis the coated substrate is dried for 5 minutes at 200° C. on ahotplate. The layer thickness is 85 nm.

Comparison Example 4.2

Production of an OLED withpolyethylenedioxythiophene/polystyrenesulfonic acid as hole-injectinglayer:

The procedure is carried out as in Comparison Example 4.1, with thefollowing variation in process step 2.:

2. Application of the Hole-Injection Layer

About 10 ml of a 1.3% polyethylenedioxythiophene/polystyrenesulfonicacid solution (Baytron® P, TP AI 4083, weight ratio PEDT:PSS of 1:6;manufacturer H. C. Starck GmbH), which had also previously been desaltedby column chromatography, are filtered (Millipore HV, 0.45 μm). TheITO-coated substrate is then placed on a paint application centrifugeand the filtered solution is distributed on the ITO-coated side of thesubstrate. The supernatant solution is then centrifuged off by rotatingthe plate at 1500 rpm for a period of 30 seconds. Following this thecoated substrate is dried for 5 minutes at 200° C. on a hotplate. Thelayer thickness is 85 nm.

The application of the metal cathodes—according to process step 4—of thelayer structures from Example 4, Comparison Examples 4.1 and 4.2, wascarried out in a joint process step in order to ensure comparability.

Results of the characterision of the OLEDs from Example 4 and ComparisonExamples 4.1 and 4.2: t = 0 t = 800 hours U/ U/ [V] *) L/[rel. units][V] *) L/[rel. units] OLED from Example 4 4.12 2.07 4.25 1.88 OLED from4.11 1.45 4.74 0.36 Comparison example 4.1 OLED from 4.24 1.55 4.84 0.45Comparison example 4.2*) Measured during the positive half-wave

The EL arrangement according to the invention with the hole-injectinglayer containing the formulation according to the invention (OLED fromExample 4) proves to be more efficient also under pulsed electricalcontrol and has a significantly longer service life than the ELarrangements with the hole-injecting layer of known material PEDT:PSS(OLEDs from Comparison Examples 4.1 and 4.2).

It is thus shown that the use of a formulation according to theinvention as hole-injecting layer in the OLED according to the inventionleads to a significantly longer service life of the OLEDs in operationcompared to OLEDs that contain hole-injecting layers of known materials(PEDT:PSS).

Example 5.1

The formulation according to the invention from Example 2.1 is used toconstruct an organic light-emitting diode (OLED). In the production ofthe OLED the same procedure as in Example 3 is adopted.

Example 5.2

The formulation according to the invention from Example 2.2 is used toconstruct an organic light-emitting diode (OLED). In the production ofthe OLED the same procedure as in Example 5.1 is adopted, except that inprocess step 2 the formulation according to the invention from Example2.2 is used.

Comparison Example 5.3

Production of an OLED withpolyethylenedioxythiophene/polystyrenesulfonic acid (PEDT:PSS) ashole-injecting layer:

The procedure is carried out as in Example 5.1, with the followingvariation in process step 2.:

2. Application of the Hole-Injection Layer

About 10 ml of a 2.8% polyethylenedioxythiophene/polystyrenesulfonicacid solution (Baytron®P, TP CH8000, weight ratio PEDT:PSS 1:20;manufacturer H. C. Starck GmbH) are filtered (Millipore HV, 0.45 μm).The ITO-coated substrate is then placed on a paint applicationcentrifuge and the filtered solution is distributed on the ITO-coatedside of the substrate. The supernatant solution is then centrifuged offby rotating the plate at 1000 rpm for a period of 30 seconds. Followingthis the coated substrate is dried for 5 minutes at 200° C. on ahotplate. The layer thickness is 80 nm.

The application of the metal cathodes—according to process step 4-of thelayer structures from Example 5.1, Example 5.2 and Comparison Example5.3, was carried out in a joint process step in order to ensurecomparability.

Results of the characterisation of the OLEDs from Examples 5.1 and 5.2as well as Comparison Example 5.3: t = 0 t = 500 hours U/[V] L/[rel.units] U/[V] L/[rel. units] OLED from Example 5.1 3.49 1.57 4.20 1.41OLED from Example 5.2 3.58 1.72 4.59 1.19 OLED from 3.68 1.68 4.82 0.54Comparison example 5.3

The voltage U and luminous intensity L, measured as photodiode current,at the start of the service life test (t=0), are compared with thecorresponding values after 500 hours (t=500 hours) under a constantcurrent load I=8 mA/cm².

The two OLEDs according to the invention from Examples 5.1 and 5.2 havelonger service lives than the OLED from Comparison Example 5.3 with theknown material PEDT:PSS in the hole-injecting layer. It is also shownthat the use of the formulation according to the invention from Example2.1 (weight ratio of PEDT:S to Nafion® of 1:6) for the production of ahole-injecting layer leads to even longer service lives of the resultingEL arrangement according to the invention in operation than when usingthe formulation according to the invention from Example 2.2 (weightratio of PEDT:S to Nafion® of 1:2.5).

Example 6

The formulations according to the invention from Example 2.3 are used toconstruct organic light-emitting diodes (OLEDs). In the production ofthe OLEDs the same procedure as in Example 3 is adopted, with thefollowing variation in process steps 1., 2. and 4.:

Instead of ITO substrates coated over the whole surface (cf. Example 3,process step 1.), structured ITO substrates are used. The ITO structuresconsist of 2.0 mm wide strips insulated from one another. Thestructuring of the ITO was carried out by a conventional photoresisttechnique followed by etching in FeCl₃ solution.

Instead of the solution from Example 2.1, in process step 2, Example 3,the solutions from Example 2.3 are used in each case.

Instead of using a perforated mask (cf. Example 3, process step 4) themetal cathode is vapour deposited through a strip mask that is alignedperpendicular to the ITO strips. The width of the strips is 1 mm. Theactive luminous area at the point of intersection of the two electrodesis 2 mm².

Comparison Example 6.1

The solution from Example 1 without addition of a further polymer isused to construct organic light-emitting diodes (OLEDs). For this, thesolids content of the solution from Example 1 is increased to 5.12. wt.% by concentration by evaporation on a rotary evaporator (PEDT-Ssolution). In the production of the OLEDs the same procedure as inExample 6 is adopted, except that the PEDT-S solution is used in processstep 2.

Results of the characterisation of the OLEDs from Example 6 andComparison Example 6.1: U = 8 V L Weight Ratio Composition of theSolution for I [rel. PEDT-S:PSS Process Step 2 [mA/cm²] units] onlyPEDT-S PEDT-S solution with solids content (S.C.) 900 4.3 · 10⁻⁶ 5.12%1:1  21.1 g of PEDT-S solution with 1.45 wt. % S.C. 900 8.0 · 10⁻⁶  5.2g of PSS solution with 5.88 wt. % S.C.,   1:2.5 10.55 g of PEDT-Ssolution with 1.45 wt. % S.C., 1000 5.0 · 10⁻⁵  6.37 g of PSS solutionwith 5.88 wt. % S.C. 1:6 10.55 g of PEDT-S solution with 1.45 wt. %S.C., 900 5.1 · 10⁻⁵ 15.61 g of PSS solution with 5.88 wt. % S.C.

The area current I and luminous intensity L of the arrangements arecompared at U=8V.

A comparison of the OLEDs from Example 6 and Comparison Example 6.1shows that an OLED with a hole-injecting layer of pure PEDT-S has lowerluminous densities at a comparable area current and thus a lowerefficiency than OLEDs with a hole-injecting layer produced from theformulations according to the invention from Example 2.3. In additionthe comparison shows that the efficiency can be significantly raised byincreasing the weight ratio of PEDT-S:SS from 1:1 to 1:2.5 or 1:6.

Although the invention has been described in detail in the foregoing forthe purpose of illustration, it is to be understood that such detail issolely for that purpose and that variations can be made therein by thoseskilled in the art without departing from the spirit and scope of theinvention except as it may be limited by the claims.

1. A composition comprising: (a) at least one polythiophene containingrepeating units of the general formula (I)

wherein, X denotes —(CH₂)_(x)—CR₁R²—(CH₂)_(y)—, wherein R¹ denotes amember selected from the group consisting of —(CH₂)_(s)—O—(CH₂)_(p)—R³and —(CH₂)_(q)—O—(CH₂CH₂O)_(r)R⁴, where R³ denotes SO₃ ⁻M⁺ or COO⁻M⁺, where M⁺ denotes H⁺, Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺ or NH₄ ⁺, s is an integerfrom 0 to 10, p is an integer from 1 to 18, R⁴ denotes C₁-C₄-alkyl, qdenotes an integer from 0 to 10, and r denotes an integer from 1 to 12,R² independently of R¹ denotes a member selected from the groupconsisting of H, a linear or branched C₁-C₂₀-alkyl radical, aC₆-C₁₄-aryl radical, —(CH₂)_(s)—O—(CH₂)_(p)R³ and—(CH₂)_(q)—O(CH₂CH₂O)_(r)R⁴,  where R³, s, p, R⁴, q and r have themeanings given for R¹, and x, y each independently denote an integerfrom 0 to 9, and (b) at least one further polymer, that is differentthat said polythiophene (a), having a moiety selected from the groupconsisting of SO₃ ⁻M⁺ groups and COO⁻M⁺ groups, in which M⁺ in each casedenotes a member selected independently from the group consisting of H⁺,Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺ and NH₄ ⁺.
 2. The composition of claim 1 wherein,M⁺ in each case denotes a member selected independently from the groupconsisting of H⁺, Na⁺ and K⁺, s is an integer from 0 to 3, p is aninteger from 2 to 6, and x, y in each case independently denote aninteger from 0 to
 3. 3. The composition of claim 1 wherein, M⁺ denotesH⁺, s denotes 0 or 1, p denotes 3, 4 or 5, and x, y in each caseindependently denote 0, 1 or
 2. 4. The composition of claim 1 wherein R²denotes H.
 5. The composition of claim 1 wherein said further polymer(b) is selected from the group consisting of a polymeric carboxylicacid, a polymeric sulfonic acid, a partially fluorinated polymercontaining sulfonic acid groups, and a perfluorinated polymer containingsulfonic acid groups, and their respective salts.
 6. The composition ofclaim 1 wherein said further polymer (b) is selected from the groupconsisting of polystyrenesulfonic acid, and a copolymer oftetrafluoroethylene and of the fluorovinylether of poly(hexafluoropropylene oxide)mono(tetrafluoro vinyl sulfonic acid)ethers and theirrespective salts.
 7. The composition of claim 1 wherein said compositioncomprises at least two further polymers (b).
 8. The composition of claim7 wherein said two polymers are polystyrene sulfonic acid and acopolymer of tetrafluoroethylene and of the fluorovinylether ofpoly(hexafluoro propylene oxide)mono(tetrafluoro vinyl sulfonicacid)ethers and their respective salts.
 9. The composition of claim 1wherein said composition has a weight ratio of said polythiophene (a) tosaid further polymer (b) of 1:2 to 1:15.
 10. The composition of claim 1further comprising at least one polar diluent.
 11. The composition ofclaim 10 wherein said polar diluent is selected from the groupconsisting of water, alcohols and mixtures thereof.
 12. The compositionof claim 10 wherein said polar diluent is selected from the groupconsisting of water, methanol, ethanol, n-propanol, 2-propanol,n-butanol and mixtures thereof.
 13. An article of manufacture selectedfrom the group consisting of hole-injecting layers in EL arrangements,hole-transporting layers in EL arrangements, organic solar cells,organic laser diodes, organic thin-film transistors, organicfield-effect transistors, electrodes and electrically conductingcoatings, wherein said article comprises the composition of claim
 1. 14.An electroluminesing arrangement comprising: a substrate, at least twoelectrode layers, at least one an emitter layer, and at least onehole-injecting layer, wherein, at least one electrode layer abuts saidsubstrate, said emitter layer is interposed between two electrodelayers, and at least one hole-injecting layer is interposed between oneof said electrode layers and said emitter layer, and further wherein,said hole-injecting layer comprises the composition of claim
 1. 15.Organic light emitting diode comprising an EL arrangement according toclaim 14.